	US 12,291,614 B2
	Fluoropolymer hybrid composite
Daniele Battegazzore, Alessandria (IT); Alberto Frache, Alessandria (IT); Julio A. Abusleme, Saronno (IT); and Giambattista Besana, Mariano Comense (IT)
Assigned to SYENSQO SA, Brussels (BE); and POLITECNICO DI TORINO, Turin (IT)
Appl. No. 17/637,472
Filed by SYENSQO SA, Brussels (BE); and POLITECNICO DI TORINO, Turin (IT)
PCT Filed Oct. 7, 2020, PCT No. PCT/EP2020/078056 § 371(c)(1), (2) Date Feb. 23, 2022, PCT Pub. No. WO2021/069469, PCT Pub. Date Apr. 15, 2021.
Claims priority of application No. 19202147 (EP), filed on Oct. 9, 2019.
Prior Publication US 2022/0282012 A1, Sep. 8, 2022
Int. Cl. C08J 5/22 (2006.01); C08F 214/22 (2006.01); H01M 10/056 (2010.01)

CPC C08J 5/2237 (2013.01) [C08F 214/225 (2013.01); H01M 10/056 (2013.01); C08F 2800/10 (2013.01); C08J 2327/16 (2013.01); H01M 2300/0065 (2013.01); H01M 2300/0091 (2013.01)]

17 Claims

1. A process for manufacturing a polymer electrolyte membrane based on a fluoropolymer hybrid organic/inorganic composite, said process comprising the following steps:

(i) providing a mixture that comprises:

a metal compound of formula (I)

X_4-mAY_m (I)

wherein m is an integer from 1 to 4, A is a metal selected from the group consisting of Si, Ti and Zr, Y is a hydrolysable group selected from the group consisting of an alkoxy group, an acyloxy group and a hydroxyl group, X is a hydrocarbon group, optionally comprising one or more functional groups,

an electrolyte solution [solution (ES)] comprising at least one metal salt [metal salt (S)] and a liquid medium [medium (L)];

optionally, at least one acid catalyst; and

optionally, an aqueous liquid medium [medium (A)];

(ii) partially hydrolysing and/or polycondensing the metal compound of formula (I) by stirring the mixture provided in step (i) until the obtainment of a solid mixture (SM) that comprises a metal compound including one or more inorganic domains consisting of =A-O-A=bonds and one or more residual hydrolysable groups Y [metal compound (M)], wherein A and Y are as above defined;

and

(iii) mixing the solid mixture (SM) provided in step (ii) with at least one fluoropolymer [polymer (F)] comprising recurring units derived from at least one fluorinated monomer [monomer (FM)] and at least one monomer comprising at least one hydroxyl group [monomer (OH)], so as to provide a solid composition (SC);

and

(iv) processing the solid composition (SC) provided in step (iii) in the molten state, so that at least a fraction of hydroxyl groups of the monomer (OH) of polymer (F) reacts with at least a fraction of residual hydrolysable groups Y of said compound (M), so as to obtain a polymer electrolyte membrane comprising a fluoropolymer hybrid organic/inorganic composite including the electrolyte solution(ES).